Waterinsoluble azodyestuffs



Patented Mar. 17,-1936 WATERINSOLUBLE AZODYESTUFFS Heinrich Morschel, Cologne-Deutz, Germany, as-

signor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application November 21, 1934, Serial No. 754,182. In Germany December 8,

8 Claims.

The present invention relates to waterinsoluble azodyestuffs and to cellulosic fibres dyed therewith, more particularly it relates to dyestufis which may be represented by the general formula:

wherein R stands for an aromatic radical free from solubilizing groups, R stands for the radical of a diazotization component free from solubilizing groups, one n stands for the number one and the other 12 stands for one of the numbers one and two.

My new dystufis are obtainable by diazotizing or tetrazotizing respectively a diazotization com; ponent free from solubilizing groups and coupling in substance or on a substratum with a 5,6,18 tetrahydro 2 hydroxynaphthalene c arb 0 xylic acid arylamide. The dyestufis prepared insubstance generally are dark brown, waterinsoluble products suitable as pigments, while those prepared on cellulosic fibres according to the usual methods of preparing ice colors generally yield brown to bordeaux to black shades of good fastness properties.

The 5,6,7,8-tetrahydro-2hydroxynaphthalene- 3-carboxylic acid arylamides used as coupling components in my invention have been described in my co-pending application for Letters Patent Serial No. 754,181, filed November 21, 1934, entitled: Dyestufi intermediates. The invention is illustrated by the following examples, without being limited thereto:

Example 1.Well boiled and dried cotton yarn is impregnated in one litre of a solution containing 2,5 grams of 3,3-dimethoxy-l.4'-di(5",6",7", 8" tetrahydro 2"-hydroxynaphthalene-3-carbonyD-aminodiphenyl, 10 ccs. of aqueous caustic soda lye of 34 B. and 10 cos. of Turkey red oil of strength, well squeezed and, without drying, introduced for about 20 minutes into one litre of a developing bath prepared in the usual manner by diazotizing 2 grams of 3-nitro-l-aminobenzene and neutralizing the excess mineral acid with sodium acetate, rinsed, soaped, again rinsed and dried. Thus is obtained a beautiful brown of good fastness properties. sponds to the following formula:

lTTOa In an analogous manner the same coupling component yields with diazotized:

5 nitro 2 amino- 1 methoxybenzene,

brown.

5-chloro-2-aminol-methylbenzene, a brown.

4-chloro-2-aminodiphenylether, a powerful reddish-brown.

a dark Example 2.20 grams of 1-(5',6',7,8'-tetra- The dyestufi correadding hot water and made up with water to one F litre. In this solution cotton tissue is impreg nated, squeezed and dried.

Part of the cotton thus impregnated is intro- 2 a N==NONO1 H on H C0NH Part of the cotton tissue impregnated in accordance with paragraph 1 of this example is printedwith a printing color prepared in the following manner:

15 grams of 5-nitro-2-amino-l-methoxybenzene are pasted with 25 cos. of warm Water and '7 grams of sodium nitrite. The paste thus obtained is slowly stirred into a mixture from 250 cos. of cold water and 26 cos. of hydrochloric acid of 32% strength. After standing for hour, a solution of 15 grams of sodium acetate in 30 ccs. of water is added, then 10 cos. of acetic acid of 50% strength are added, and the solution thus obtained is stirred into 500 grams of starch tragacanth thickener and made up with Water to- 1 kg. The print is dried, boiled in one litre of a bath containing 2 cos. of aqueous caustic soda lye of 38 B. and 2 ccs. of water glass, rinsed, soaped in a boiling bath, again rinsed and dried. A brownish-black is thus obtained. The dyestuff corresponds to the following formula:

OCH:

Example 3.Cotton tissue is printed with a printing color prepared in the following manner:

6.5 grams of the diazoamino compound prepared from diazotized 2-chloro-4-benzoylamino- 5-methoxy-1-aminobenzene and 4-sulfo-2-methylaminobenzoic acid and 3.1 grams of 2-(5', 6', 7, 8'-tetrahydro 2'- hydroxynaphthalene 3- carbonylamino) -1ethoxybenzene are pasted with a mixture from 3 cos. of spirit, 3 cos. of aqueous caustic soda lye of 38 B. and 15 cos. of water, the paste is slightly heated and stirred into 50 grams of a neutral starch tragacanth thickener and made up with water to 100 grams.

The print is dried, steamed for 5 minutes with steam containing acetic and formic acid, rinsed, soaped in a boiling bath, again rinsed and dried. Thus is obtained a powerful yellowish-brown. The dyestufi corresponds to the following for- H on 00113 In the following table there are given some combinations prepared in accordance with the present invention and the shades obtained therewith on cotton:

Coupling component Diazotization component Shade 1 (5,6,7,8 tetrahydro 2 hydroxynaphthalene-3-carbonylamino) -2-methoxybenzene Do -4-methoxybenzene Do -2-ethoxybenzene De -2-methyl-4methoxybenzene Do -2-methy1benzene Do -2,5-dimethoxybenzene 2 chloro benzoylamino 5 methoxyl-aminobenzene 5-nitro-2-amino-l-Inethoxybenzene 4-amino-3,2-dimethylazobenzene 2 chloro 4 benzoylamino- 5 methoxy-l-aminobenzene 4-amino-3,2-dimethylazobenzene 4-nitro-l-naphthylamine 5-nitro-2-amino-1,4-dirnethoxybenzene 4 amino 2,4 dimethyl 5 methexy-2-nitroazobenzene 4-amino-2,3-dimethy1azobenzene 2 nitro 4 methoxy 5 amino 1 methylbenzene 4-nitro-l-naphthylamine 5-nitro-2-amino-l-methoxybenzene Do.-- 2-(5',6,7,8 hydro ynaphthalene 3 carbonylamino) naghthalene Do 1,5-di- (5',6,7,8 tetrahydro 2' hydroxyuaphthalene-3-carbonylamino)- naghthalene 4,4! dl (5,6,7,8- tetrahydro-2- hydroxynaphthalene 3 carbony1- amino)- -3,3igimethoxydiphenyl o -3, 3-dimethyldiphenyl naphthalene 3 carbonylamino diphenyleneoxide l-aminoanthraquinone 4,4-dichlor0-2-amino-diphenylether 4, 5-dichloro-2-aminodiphenylether.

2-nitro-4-methoxy-5-a1nino-l-methy1- benzene fi-nitro-Z-amino-l-methoxybenzene 5-nitro-2-amino-l,4-dimethoxybenzene- 4-chlore-Z-aminodiphenylether 1-methoxy-2-aminobenzene-4-su1lodiethylamide 5-chloro-2-amlno-l-methylbenze 4amin0-4-n1ethoxydiphenylamine 2-amino-5-benzoylamino-1,4-diethoxybenzene l-aminoanthraquinone 3-nitraniline 3-nitro-4-amino-l-methoxybenzene l-aminocarbazole 2-(4-z11minopheny1)-5-methylbenzothiaz e 2-chloro-4-benzoylamino- 5 -methoxy-1- aminobenzene Z-aminodiphenylsulfone 3-Inethoxy-4-aminodiphenylamine 2-chloro-4-benzoylamino-5-I.nethoxy-laminobenzene Yellowish-brown Blackish-green Blackish-brown Yellowish-brown Blackish-brown 0 Yellowish dark brown Reddish-brown Blaokish-brown Dark brown Reddish blackish brown 45 Brownish-black Reddish blackishbrown Gteenish-black Blackish-grey Greenish-black 50 Violet black Reddish-brown Reddish-brown Deep bordeaux Violet dark brown Reddish brown Do. Blackish-violet 60 Violet brown Brown Reddish-brown Brown Dark brown Yellowish-brown Reddish-brown Yellowish-brown Orange brown Reddish-brown Yellowish-brown i claim: 1. Waterinsoluble azodyestufis of the general formula:

wherein R stands for a radical of the benzene or naphthalene series free from solubilizing groups and R stands for a radical of the benzene series free from solubilizing groups, yielding, when produced on the fibre, generally brown to black shades of good fastness properties.

3. Waterinsoluble azodyestufis of the general formula:

wherein R stands for a radical of the benzene or naphthalene series free from so-lubilizing groups and R stands for a radical of the benzene series free from solubilizing groups containing a nitro group in p-position to the azo bridge, yielding, when produced on the fibre, generally brown to black shades of good fastness Properties.

4. The dyestufi of the following formula:

O O NH8 2 yielding, when produced on the fibre, violet blackish-brown shades of good fastness properties.

5. Fibres dyed with a .dyestuff as claimed in claim 1.

6. Fibres dyed with a dyestuff as claimed in claim 2.

7. Fibres dyed with a dyestufi as claimed in claim 3.

8. Fibres dyed with the dyestuff as claimed in claim 4.

HEINRICH MORSCI-IEL. 

